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Photochemistry of Tricyclo[5.2.2.0 2,6 ]undeca‐4,10‐dien‐8‐ones: An Efficient General Route to Substituted Linear Triquinanes from 2‐Methoxyphenols. Total Synthesis of (±)‐Δ 9(12) ‐Capnellene
Author(s) -
Hsu DayShin,
Chou YuYu,
Tung YenShih,
Liao ChunChen
Publication year - 2010
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200902752
Subject(s) - cyclopentadiene , chemistry , adduct , yield (engineering) , enone , stereochemistry , organic chemistry , medicinal chemistry , physics , catalysis , thermodynamics
An efficient and short entry to polyfunctionalized linear triquinanes from 2‐methoxyphenols is described by utilizing the following chemistry. The Diels–Alder reactions of masked o ‐benzoquinones, derived from 2‐methoxyphenols, with cyclopentadiene afford tricyclo[5.2.2.0 2,6 ]undeca‐4,10‐dien‐8‐ones. Photochemical oxa‐di‐π‐methane (ODPM) rearrangements and 1,3‐acyl shifts of the Diels–Alder adducts are investigated. The ODPM‐rearranged products are further converted to linear triquinanes by using an O ‐stannyl ketyl fragmentation. Application of this efficient strategy to the total synthesis of (±)‐Δ 9(12) ‐capnellene was accomplished from 2‐methoxy‐4‐methylphenol in nine steps with 20 % overall yield.